EP2482671B1 - Revêtement fertilisant - Google Patents

Revêtement fertilisant Download PDF

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Publication number
EP2482671B1
EP2482671B1 EP10763060.0A EP10763060A EP2482671B1 EP 2482671 B1 EP2482671 B1 EP 2482671B1 EP 10763060 A EP10763060 A EP 10763060A EP 2482671 B1 EP2482671 B1 EP 2482671B1
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EP
European Patent Office
Prior art keywords
cross
catalyst
coating composition
fertilizer
coating
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EP10763060.0A
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German (de)
English (en)
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EP2482671A1 (fr
Inventor
Stefan Hendrikus Schaafsma
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Stamicarbon BV
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Stamicarbon BV
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00—Fertilisers characterised by their form
    • C05G5/30—Layered or coated, e.g. dust-preventing coatings
    • C05G5/37—Layered or coated, e.g. dust-preventing coatings layered or coated with a polymer
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/10—Organic substances
    • A23K20/158—Fatty acids; Fats; Products containing oils or fats
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K40/00—Shaping or working-up of animal feeding-stuffs
    • A23K40/30—Shaping or working-up of animal feeding-stuffs by encapsulating; by coating
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00—Fertilisers characterised by their form
    • C05G5/30—Layered or coated, e.g. dust-preventing coatings

Definitions

  • the invention relates to a process for the coating for fertilizers and animal feed and in particular biodegradeable coatings which exhibit good anti-caking properties.
  • a disadvantage of the known coating agents for fertilizers is that, after the field application of the fertilizer, the coating agents stay in the soil and accumulate. Therefore, the known coating agents are harmful for the environment.
  • Another disadvantage of conventional coatings is that they often contain highly purified and processed compounds, many of which are synthetic, which possess a high carbon footprint and thus are environmentally unsustainable.
  • US 3,321,298 discloses coated water-soluble fertilizer and method of making the same.
  • the coated fertilizer are prepared by tumbling a mixture of tung oil and catalyst for 15 minutes at a temperature between 65 and 93°C and then 15 minutes post-heating at 93°C; the catalyst employed is 0.06 wt% manganese or 0.03 wt% cobalt or 0.24 wt % lead.
  • the coated fertilizer may also contains 0.5 wt% of mineral filler such as talc. The total amount of coating in the fertilizer is 9 wt%.
  • GB 202 523 A discloses slow release fertilizer coated with a water insoluble polymer possessing a three dimensional structure.
  • the polymer is a cross-linked unsaturated oil having 12-20 carbon atoms.
  • Suitable oils have a viscosity from a few centipoise to 50,000 centipoise and are for example linseed oil, sunflower oil, dehydrated castor oil, soya oil etc...
  • Catalyst such as peroxides, diazo compounds and known metal salts are added to the oil to accelerate the polymerisation in amount between 0.4 wt% to 2 wt%.
  • the first coating applied has a viscosity of at least 40 000 cP in the prepolymerized stage. Further coatings with a lower viscosity are applied to cover and seal any defect on the granule surface.
  • the present invention addresses at least some of the abovementioned problems, through a process for coating a fertilizer or animal feed particulate comprising the steps of:
  • the coating composition applied in the process of the present invention has improved long term anti-caking tendencies compared to conventional biodegradable coating compositions.
  • the coating composition comprises between 0 and 40 wt % biomass with the median particle size (D 50 ) between 0 and 250 ⁇ m.
  • D 50 median particle size
  • the addition of biomass has been found to further enhance the long term anti-caking properties of the coating formulation.
  • the coating composition comprises at least 60 wt%, more preferably at least 70 wt%, even more preferably at least 80 wt% and most preferably at least 90 wt% of a cross-linked lipid.
  • the cross-linked lipid preferably has a viscosity at 20°C of at least 120 mPa.s., more preferably at least 150 mPa.s., even more preferably at least 170 mPa.sec. and most preferably at least 200 mPa.s.
  • Cross-linked lipids with a lower viscosity at 20°C have been found to have inferior anti-caking properties after storage over a prolonged period (e.g. 30 days).
  • the cross-linked lipid preferably has a viscosity at 20°C of at no more than 800 mPa.s., more preferably no more than 600 mPa.s., even more preferably no more than 500 mPa.sec. and most preferably no more than 400 mPa.s.
  • Cross-linked lipids with a higher viscosity at 20°C are more difficult to handle and apply to particulates, such as fertilizer particulates.
  • the level of catalyst in the coating composition is preferably less than 0.15 wt%, more preferably less than 0.10 wt%, even more preferably less than 0.05 wt% and most preferably less than 0.02 wt% relative to the weight of the lipid.
  • the catalyst will be detectable in the coating composition and thus its content will be greater than 0.00 wt%. In general, the lower the level of catalyst in the coating composition, the more environmentally friendly it is.
  • the process of the present invention provides a fertilizer or animal feed particulate comprising the aforementioned coating composition.
  • the coating composition represents at least 0.01 weight %, more preferably at least 0.05 wt%, even more preferably least 0.10 wt% and most preferably at least 0.15 wt% relative to the total weight of the particulate. At lower levels, the coating composition does not significantly affect the anti-caking properties of the particulates.
  • the coating composition represents no more than 1.0 wt%, more preferably no more than 0.8 wt%, even more preferably no more than 0.6 wt% and most preferably no more than 0.4 wt% relative to the total weight of the particulate.
  • Anti-caking performance is not further improved with a higher proportion of the coating composition.
  • the coating composition comprises or is derived from at least 60 wt%, more preferably at least 70 wt%, even more preferably at least 80 wt% and most preferably at least 90 wt% of unsaturated lipid relative to the total weight of the coating composition.
  • the cross-linking of the unsaturated lipid preferably results in an increase in the viscosity of the resulting coating composition relative to the pre-cross linked coating composition of at least 20%, more preferably at least 50% and most preferably at least 100%.
  • the cross-linking reaction is carried out during the application of the coating to the particulate, thereby necessitating a relatively quick reaction time.
  • a quick reaction time e.g. less than 30 minutes
  • the quantity of the catalyst may be minimized, thereby enabling the amount of less environmentally friendly catalysts to be reduced or eliminated.
  • less active, but more environmentally friendly catalysts e.g. an iron based or enzymatic catalyst
  • the cross-linking reaction takes place at an ambient temperature (e.g. about 23°C) in air over a period of at least 2 hours, more preferably at least 12 hours, even more preferably at least 24 hours, and most preferably at least 48 hours.
  • an ambient temperature e.g. about 23°C
  • reaction times at preferably less than 2 weeks and more preferably less than 1 week.
  • step (b) a preceding step is included which substantially terminates the cross-linking or chain extending reaction of step (a), once the desired viscosity is reached, to thereby produce a coating composition.
  • Substantial termination of the cross-linking reaction is to be given a purposive construction, with residual cross-linking reaction due to residual catalyst activity or through non-catalytic reaction encompassed within the meaning of substantial termination.
  • substantial termination of the cross-linking reactions results in no more than a 50% increase in viscosity at 20°C of the coating composition being saturated in air at ambient temperature (e.g. about 23°C) for 48 hours. More preferably the increase in viscosity is no more than 30%, even more preferably no more than 20 %, and most preferably no more than 10 %. The lower the % change in viscosity, the greater the ability of the coating composition to be stored prior to application without significant changes in viscosity. This results in a product with a more consistent viscosity enables more efficient and effective application of the coating to the particulates.
  • the termination of the cross-linking reaction may be carried out by any suitable method.
  • the termination of the cross-linking reaction is carried out through the substantial removal of the catalyst.
  • the catalyst system is preferably a heterogenous catalyst system (e.g. a solid catalyst and liquid reactant).
  • the cross-linking reaction is substantially terminated through the addition of a catalyst deactivating agent.
  • a cross-linking reaction for the purposes of the present inventions, is inclusive of chain extending reactions.
  • Environmentally friendly means that, from a life cycle analysis, the process or product uses fewer resources (energy and/or materials) or releases fewer harmful substances compared to most, if not all, conventional processes or products.
  • the coating composition applied in the process of the invention comprises between 0 and 40 wt% biomass and more preferably between 10 and 30 wt% biomass.
  • the coating composition comprises between 50 and 90 wt% and more preferably between 60 to 85 wt.% cross-linked lipids, as defined within the scope of the present invention.
  • the coating essentially consists of the cross-linked lipids.
  • the unsaturated lipids preferably comprise an unsaturated fatty acyl and more preferably comprise an ester of glycerol, such as a natural fat or oil (e.g. vegetable or animal derived fats and oils).
  • a natural fat or oil e.g. vegetable or animal derived fats and oils.
  • the lipids comprise unsaturated fatty acids having between 12 and 20 carbons.
  • the lipids comprise unsaturated fatty acids derived as a byproduct of bio-diesel production.
  • the degree of unsaturation of the lipids is preferably at least 60, more preferably at least 70, even more preferably at least 80, yet even more preferably at least 90 and most preferably at least 100.
  • the higher iodine value the greater degree of unsaturation (i.e unsaturated bonds) in the lipids and therefore the greater the propensity of the lipids to cross-link.
  • any suitable known catalyst which cross-links the unsaturated lipid may be used.
  • the catalyst is selected from the group consisting of peroxides, azo, preferably diazo, compounds and inorganic and organometallic compounds.
  • Preferred inorganic and organometallic catalysts preferably comprise manganese, lead, zinc, iron, zirconium, calcium, potassium, zinc, vanadium, cobalt and combinations thereof. More preferably, the catalyst comprises iron.
  • the organometallic compounds are preferably naphthenates, carboxylate, octoates, oleates, linoleates, and resinates.
  • the quantity of catalyst is expressed in relation to the active component (e.g. the metal component, such as cobalt, rather than the organometallic component which it may form part of).
  • the catalyst is a heterogeneous catalyst.
  • the catalyst is preferably a solid catalyst. More preferably, the catalyst is supported on an inert support material (e.g. silica).
  • the solid catalyst may be in the form of free particulates, in which case the removal of the catalyst is performing using conventional solid liquid separation techniques, such as a filtration operation.
  • the solid catalyst may form a fixed bed in a reaction vessel. In this embodiment, the unsaturated lipids are circulated around the reaction vessel for the required length of time before being removed from the reaction vessel.
  • the activity of the catalyst in a solid form may be less compared to liquid catalysts, the ability to reuse the solid catalyst enhances its environmentally friendly characteristics.
  • any suitable catalyst deactivating agent which substantially terminates the cross-linking reaction may be used.
  • the catalyst deactivating agent performs a dual function within the coating composition, such to minimize the complexity and environmental footprint of the coating composition.
  • the catalyst comprises a metal selected from the group consisting of manganese, lead, zinc, iron, zirconium, calcium, potassium, zinc, vanadium and/or cobalt and the deactivating agent comprises an amine.
  • the specific amine may be readily determined by those skilled in the art.
  • the catalyst deactivating agent comprises an alkyl substituted amine and more preferably a fatty acid amine.
  • Fatty acid amine may be also used in the coating composition to promote the adhesion of inert inorganic fillers to the particulate, such as talc or bentonite.
  • catalyst deactivating agents include sodium or potassium hydroxide and other strong bases.
  • the catalyst deactivating agent is an inert atmosphere (i.e. substantially free of oxygen) which prevents the progression of the cross linking reaction (e.g. nitrogen or carbon dioxide) prior to application to the coating onto the particulates.
  • the biomass particles are preferably plant derived solid particles, which are preferably oilseed meal, although small particles of any plant or vegetable source (eg. grains) may be suitable, including fibres, saw dust, scrap meal or flour, such as flour of wheat, barley, legumes, wood dust, coconut or alfalfa.
  • the oilseed meal is preferably derived from the same oilseeds used to derive the oil component of the biomass composition, such that the coating biomass composition may be produced within the same oilseed processing facility, thus reducing transport and storage costs.
  • the oilseeds meal is typically high in protein (about 10 to 30 wt%) and thus this source of biomass not only degrades into the environment, but may also contribute to the efficacy of the fertilizer (although any contribution will be relatively small).
  • the biomass composition is used to coat animal feed, the plant derived oil contributes to the energy value of the animal feed, while the plant derived solid particles contribute to the protein content of the animal feed.
  • the biomass solid particles are rigid, such that the particles may be ground into the target particle size distribution.
  • the oilseed meal is substantially free of husks or other fibrous material which may be difficult to grind to the target particle size range. Ground de-hulled rapeseed has been found to be particularly effective within the scope of the present invention.
  • the biomass solid particles should have a relatively low moisture and moisture uptake rate.
  • the initial moisture of the biomass solid particles are preferably less than 30 wt.%, more preferably less than 20 wt%, even more preferably less than 12 wt% and most preferably less than 5 wt%.
  • Biomass derived from grains and/or legumes generally conform to the requirements of good mechanical and moisture absorption properties and, as such, are preferred compared to biomass derived from yeast or fungi which have less suitable mechanical and water absorption properties.
  • the biomass solids content such as plant derived solid particles may be measured by their hexane insoluble content which therefore excludes oil and other hexane soluble material such as phospholipids.
  • biomass solid contents may be derived by difference, after the oil (hexane soluble) and moisture (analyzed by Karl Fischer technique) components are calculated.
  • the solids are preferably non-elastic such to enable efficient and effective grinding of the biomass to the desired particle size range.
  • the de-oiled oilseed meal typically contains 1 to 15 wt% residual oil and 5 to 15 wt% moisture relative to the total weight of the de-oiled oilseeds, depending upon the oil extraction means used.
  • the determined % wt oil will be inclusive of other hexane soluble material such as waxes and phospholipids. Separate analysis of these oil miscible components may be performed using standard industry techniques. Standard industry techniques include those published by the American Oil Chemist's Society (AOCS).
  • the solid biomass particles may also be sourced from:
  • the solid biomass particles of the first group can, for instance, be either the microorganisms as such or the fraction of yeast cells, bacteria cells and/or fungi cells which is insoluble in water and which is obtained by opening of yeast cells, bacteria cells and/or fungi cells by a physical, mechanical, chemical or enzymatic method (or a combination of two or more of these methods) with consequent release of the content of the yeast cells, bacteria cells or fungi cells and by recovering the insoluble fraction.
  • the microorganisms are preferably biologically inert.
  • biomass particles may be found in WO2008/000492 and WO2009/074679 .
  • the coating composition may comprise other components, such as waxes, fatty amines, paraffines, sulfonates, aldehydes or urea-aldehyde resins.
  • Inert inorganic fillers such as talcum, lime, kaolin and kieselguhr are preferably applied to the coated particulates to enhance handling properties.
  • the proportion of inert fillers is preferably between 0 and 2 wt% and more preferably between 0.2 and 1.0 wt% relative to the total weight of the coated particulate and inert filler.
  • the particle size distribution of the inert filler, such that the D 50 is between 5 and 100 microns and more preferably between 10 and 40 micron. Most preferably, no inorganic fillers are added to the coating composition.
  • a fertilizer that is suitable to be coated with the coating composition is any solid fertilizer comprising particles with a diameter of 0.5-50 mm; preferably with a diameter of 1 - 5 mm.
  • fertilizers are calcium nitrate, ammonium nitrate, calcium ammonium nitrate (CAN), ammonium sulfate nitrate, ammonium sulfate, urea, superphosphate, triple superphosphate, monoammonium phosphate, diammonium phosphate, ammonium polyphosphate, nitrophosphate, potash, potassium phosphate, potassium nitrophosphate, NPK fertilizers and combinations of these fertilizers. These fertilizers can be produced by granulation, prilling and flaking.
  • the fertilizer is granular urea or calcium ammonium nitrate (CAN), because these fertilizers are produced and utilized in large quantities and caking during storage and transport is, for these fertilizers, a big problem.
  • CAN calcium ammonium nitrate
  • the animal feed includes granules and pellets and other particulate forms of animal feed, which are used and known within the commercial livestock industry.
  • the granules and pellets have a typical diameter of 1 to 50 mm; and in particular 2 to 20 mm.
  • the coated fertilizer or animal feed can be produced by addition (e.g. by spraying or dripping) of the coating composition on the particulates in, for instance, a pan granulator, a rotating drum or a fluid bed apparatus.
  • the coating composition is applied as a single layer.
  • the coating is applied to the fertilizer via conventional techniques, such as spraying the biomass composition on the fertilizer (or animal feed) particles in rotating drum or coating pan.
  • the coating preferably has a moisture content of less than 5 wt% relative to the total weight of the coating composition. More preferably the moisture content is less than 3 wt % and even more preferably less than 1 wt% relative to the total weight of the coating composition.
  • the majority of the water is stabilized, such that it is not available to be transferred between coated particles.
  • the moisture may be bound within the solid biomass or contained by a hydrophobic oil or wax barrier.
  • coated fertilizer provided by the process of the invention, for instance coated urea particles, as cattle feed instead of as a fertilizer.
  • a coating composition for a fertilizer comprising:
  • the coated particulates provided by the process of the present invention have a caking tendency of less than 0.08 MPa, more preferably less than 0.05 MPa and even more preferably less than 0.025 MPa after 15 days storage using the methodology described in the examples.
  • the particle size of the biomass was determined according to ISO 13320-1.
  • the particle size distribution of the fertilizer or animal feed was determined according to ISO-DIS 8397 and ISO 565.
  • the D 50 is the theoretical sieve opening, having such a mesh size that 50 wt % of the fertilizer or animal feed particles is larger and 50 wt% of the fertilizer or animal feed particles is smaller than this mesh size.
  • the D 90 is determined in an analogous way.
  • Viscosity was determined using a Paar Physica MCR 300 rheometer with a CC27 measuring geometry. Measurements were performed at 20 degrees Celsius (°C) and 50 °C after the sample was maintained at a shear rate of 100 sec -1 for 15 mintues at each temperature.
  • the caking test was performed as follows:
  • the canola oil and catalyst (0.12 wt% of NuodexTM Cobalt 8 relative to the total weight of the coating composition, which equates to 0.01 wt%, 0.015 wt% and 0.13 wt% cobalt (i.e. catalyst component) relative to the weight of the oil, for examples 1 to 3 respectively) are combined, saturated with air and stirred at ambient temperature for 48 hours.
  • the viscosity at 20°C of the cross-linked canola oil had risen from 68 to 172 mPa.sec (Table 2).
  • the effect of cross-linking on viscosity is less at 50°C, with a small difference in viscosity observed between the reacted (catalyst), unreacted (no catalyst) and deactivated (catalyst + catalyst deactivating agent) compositions.
  • This effect enables the cross-linked oil to be conveniently applied at substantially the same temperature as conventional coating compositions.
  • fatty acid amine (4.4 wt% relative to the total weight of the composition) was dissolved in the cross-linked canola oil at 50°C to thereby deactivate the catalyst.
  • the coating composition was heated to about 80 °C.
  • the coating composition was then sprayed onto 1.5 kg of fertilizer particles that were kept moving in a rotating drum (35 rpm, diameter 25 cm, length 15 cm) at a temperature of 35 °C.
  • the coating composition represented 0.18 wt% of the total weight of the coated fertilizer.
  • the coating compositions exhibited good anti-caking properties over a 30 day storage period compared to composition in which insufficient cross-linking had occurred (comparative experiment A), or in which no coating was applied (comparative experiment B), or in which no catalyst was applied (comparative experiment C).
  • Anti-caking performance was particularly good for coating compositions comprising 30 wt% biomass (examples 2 & 3), in which the anti-caking performance remained substantially constant between 2 and 30 days storage.
  • Table 1 Example Biomass Wt% Biomass Catalyst (wt%) Coating (wt%) Caking tendency (MPa) 2 days 7 days 15 days 21 days 30 days 1 - - 0.010 0.18 0.010 0.009 0.011 - 0.045 2 Sawdust 16 0.013 0.18 0.009 0.008 0.008 - 0.011 3

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Zoology (AREA)
  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Pest Control & Pesticides (AREA)
  • Organic Chemistry (AREA)
  • Animal Husbandry (AREA)
  • Fertilizers (AREA)

Claims (6)

  1. Procédé pour le revêtement d'une matière particulaire de fertilisant ou d'alimentation pour animaux comprenant les étapes :
    a. de formation d'une composition de revêtement par réticulation d'un lipide insaturé en présence d'un catalyseur jusqu'à ce que la viscosité du lipide réticulé à 20°C se trouve dans l'intervalle de 110 à 800 mPa.s ; et
    b. d'application de la composition de revêtement à la matière particulaire,
    dans lequel la composition de revêtement comprend et/ou est dérivée d'au moins 50 % en masse de lipide insaturé,
    dans lequel entre les étapes (a) et (b) la réaction de réticulation de l'étape (a) est pratiquement terminée.
  2. Procédé selon la revendication 1, dans lequel la réticulation de l'étape (a) a lieu sur une période d'au moins 2 heures.
  3. Procédé selon l'une quelconque des revendications 1 ou 2, dans lequel l'addition d'un désactivateur de catalyseur termine pratiquement la réaction de réticulation de l'étape (a).
  4. Procédé selon la revendication 3, dans lequel le désactivateur de catalyseur comprend un groupe amine.
  5. Procédé selon l'une quelconque des revendications précédentes, dans lequel la réticulation du lipide insaturé résulte de préférence en une augmentation de la viscosité de la composition de revêtement résultante par rapport à la composition de revêtement pré-réticulée d'au moins 20 %.
  6. Procédé selon l'une quelconque des revendications précédentes, dans lequel l'élimination du catalyseur du produit de l'étape (a) termine sensiblement la réaction de réticulation.
EP10763060.0A 2009-09-28 2010-09-28 Revêtement fertilisant Active EP2482671B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP10763060.0A EP2482671B1 (fr) 2009-09-28 2010-09-28 Revêtement fertilisant

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP09171518A EP2301366A1 (fr) 2009-09-28 2009-09-28 Revêtement fertilisant
PCT/NL2010/050632 WO2011037469A1 (fr) 2009-09-28 2010-09-28 Revêtement pour engrais
EP10763060.0A EP2482671B1 (fr) 2009-09-28 2010-09-28 Revêtement fertilisant

Publications (2)

Publication Number Publication Date
EP2482671A1 EP2482671A1 (fr) 2012-08-08
EP2482671B1 true EP2482671B1 (fr) 2016-09-14

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EP09171518A Ceased EP2301366A1 (fr) 2009-09-28 2009-09-28 Revêtement fertilisant
EP10763060.0A Active EP2482671B1 (fr) 2009-09-28 2010-09-28 Revêtement fertilisant

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EP09171518A Ceased EP2301366A1 (fr) 2009-09-28 2009-09-28 Revêtement fertilisant

Country Status (8)

Country Link
US (1) US8845775B2 (fr)
EP (2) EP2301366A1 (fr)
CN (1) CN102595926B (fr)
CA (1) CA2774874C (fr)
EA (1) EA021274B1 (fr)
LT (1) LT2482671T (fr)
PL (1) PL2482671T3 (fr)
WO (1) WO2011037469A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9688586B1 (en) * 2016-09-11 2017-06-27 Aicardo Roa-Espinosa Modified fertilizer and a method of manufacturing thereof
BR112021014151A2 (pt) * 2019-01-17 2021-09-21 The Mosaic Company Revestimentos hidrofóbicos para melhorar os parâmetros de qualidade física de fertilizantes
US11192830B2 (en) * 2020-04-15 2021-12-07 Innovations for World Nutrition, LLC Seed coating to promote plant growth and method of increasing plant yield

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999063817A1 (fr) * 1998-06-09 1999-12-16 Oms Investments, Inc. Engrais pre-enrobes a liberation controlee et procede de preparation de ces derniers
WO2008000492A2 (fr) * 2006-06-30 2008-01-03 Dsm Ip Assets B.V. Engrais enrobé
EP2070893A1 (fr) * 2007-12-13 2009-06-17 DSMIP Assets B.V. Fertilisant revêtu amélioré

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3321298A (en) * 1964-03-20 1967-05-23 Sr Verne C Bidlack Tung oil encapsulated controlled release water-soluble fertilizer
IL81975A0 (en) * 1987-03-24 1987-10-20 Haifa Chemicals Ltd Method for the manufacture of slow-release fertilizers
US5230913A (en) * 1991-03-01 1993-07-27 Nabisco, Inc. Fat mimetic having mineral core with fatty coating
US6391454B1 (en) * 1999-04-06 2002-05-21 Agway Inc. Controlled release urea-based products
US6540808B2 (en) * 2001-04-09 2003-04-01 Mississippi Chemical Corporation Controlled release fertilizers based on self-assembled molecule coatings

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999063817A1 (fr) * 1998-06-09 1999-12-16 Oms Investments, Inc. Engrais pre-enrobes a liberation controlee et procede de preparation de ces derniers
WO2008000492A2 (fr) * 2006-06-30 2008-01-03 Dsm Ip Assets B.V. Engrais enrobé
EP2070893A1 (fr) * 2007-12-13 2009-06-17 DSMIP Assets B.V. Fertilisant revêtu amélioré

Also Published As

Publication number Publication date
EA021274B1 (ru) 2015-05-29
CA2774874C (fr) 2016-07-05
EP2301366A1 (fr) 2011-03-30
LT2482671T (lt) 2016-12-12
PL2482671T3 (pl) 2017-02-28
EA201270494A1 (ru) 2012-09-28
US20130055776A1 (en) 2013-03-07
CA2774874A1 (fr) 2011-03-31
CN102595926B (zh) 2014-06-11
EP2482671A1 (fr) 2012-08-08
US8845775B2 (en) 2014-09-30
CN102595926A (zh) 2012-07-18
WO2011037469A1 (fr) 2011-03-31

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